EP3401001A1 - Procédé et installation destinés à séparer des gaz associés à partir de gaz brut de synthèse - Google Patents

Procédé et installation destinés à séparer des gaz associés à partir de gaz brut de synthèse Download PDF

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Publication number
EP3401001A1
EP3401001A1 EP17400026.5A EP17400026A EP3401001A1 EP 3401001 A1 EP3401001 A1 EP 3401001A1 EP 17400026 A EP17400026 A EP 17400026A EP 3401001 A1 EP3401001 A1 EP 3401001A1
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EP
European Patent Office
Prior art keywords
absorbent
methanol
adsorbent
synthesis gas
loaded
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17400026.5A
Other languages
German (de)
English (en)
Inventor
Matthias Linicus
Sandra Jensen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to EP17400026.5A priority Critical patent/EP3401001A1/fr
Priority to DE202017107744.6U priority patent/DE202017107744U1/de
Priority to PCT/EP2018/025130 priority patent/WO2018206154A1/fr
Priority to CN201820691524.3U priority patent/CN209242962U/zh
Priority to CN201810441588.2A priority patent/CN108863720A/zh
Publication of EP3401001A1 publication Critical patent/EP3401001A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2021—Methanol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a process for the separation of associated gases from a Rohsynthesegasstrom by washing the Rohsynthesegasstroms with a liquid, physically acting absorbent, wherein the absorbent is driven in a cyclic process in which it loaded during washing with associated gases, then by reducing the pressure, flashing and / or Desorbed and then reused for washing the Rohsynthesegasstroms warming.
  • the invention also relates to a system for operating the method.
  • Rectisol method As the Rectisol method are known.
  • the Rectisol procedure is in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed. Vol. 15, p. 399 ff , basically described.
  • This process serves to purify crude synthesis gas produced from coal or coke by the fixed-bed pressure gasification process, consisting mainly of CO and H 2 , by absorbing the accompanying gases.
  • the fixed bed pressure gasification process is in Ullmann's Encyclopaedia of Industrial Chemistry, 6th ed. Vol. 15, p. 367ff basically described.
  • the Rectisol process uses methanol as the absorbent, exploiting the property of the methanol that its absorbent capacity for impurities increases greatly with decreasing temperature, while remaining practically constant for CO and H 2 .
  • the undesirable accompanying substances are mainly the accompanying gases carbonyl sulphide (COS), hydrogen sulphide (H 2 S) and carbon dioxide (CO 2 ).
  • the methanol used as absorbent is circulated in this process via regeneration systems.
  • the loaded methanol is released from the absorbed gases by physical means.
  • CO 2 is preferably removed by pressure release and / or stripping with a gas, for example nitrogen, from the loaded methanol absorbent.
  • the sulfur-containing gases, COS and H 2 S are driven off by heating. The aim is to produce a COS / H 2 S gas which is as low in CO 2 as possible, since its economically interesting further processing is impaired by mixing with CO 2 .
  • the Rectisol procedure distinguishes between the standard and selective Rectisol procedures.
  • the accompanying gases COS / H 2 S and the CO 2 are separated together from the crude synthesis gas in one absorption step.
  • the sulfur-containing accompanying gases COS / H 2 S and CO 2 are separated from the crude synthesis gas in separate, successive absorption steps.
  • This selective absorption is made possible by suitable adjustment of the process parameters, in particular the ratio of absorbent and gas to be absorbed.
  • the advantage of selective absorption is that most of the COS / H 2 S and CO 2 gas is separated during absorption, and only the smaller part has to be separated in the regeneration of the methanol.
  • the crude synthesis gas also contains other associated gases.
  • the publication DE 10 2006 056 117 A1 describes a corresponding method in which the absorption steps for the separation of the sulfur components and the CO 2 is preceded by a further absorption step to selectively separate metal carbonyls from the synthesis gas.
  • the synthesis gas stream contains too high an amount of mercaptans (C1-C4) and other undesired, less volatile, but in the absorbent methanol very readily soluble sulfur components, e.g. Thioethers and / or thiophenes, these can accumulate in the methanol and are not sufficiently removed from the methanol in the hot regenerator due to their low vapor pressure and high solubility in methanol. Too much of these trace amounts make the methanol useless for the wash because it can contaminate the washed syngas stream.
  • a known way to avoid the accumulation of undesirable components in the absorbent is to replace a correspondingly large part of the absorbent continuously, the case discharged part is disposed of.
  • the object of the invention is to provide a method which avoids the disadvantages of the prior art described above.
  • the object is achieved by a method according to claim 1 and by a system according to claim 7.
  • a process for the separation of associated gases from a Rohsynthesegasstrom by washing the Rohsynthesegasstroms with a liquid, physically acting absorbent wherein the absorbent is driven in a cyclic process in which it is loaded with accompanying gases during washing, then desorbed by depressurization, flashing and / or heating and then is reused for washing the Rohsynthesegasstroms, characterized in that as a further measure in addition to the desorption at least a portion of the absorbent is passed through an adsorbent-containing solid body.
  • Fluid communication between two regions of the reactor according to the invention is understood to mean any type of compound which allows a fluid, for example the feed gas stream or the synthesis gas product stream, to flow from one to the other of the two regions irrespective of any intervening regions or components.
  • the invention enables an extension of the life of the absorbent. This saves costs for fresh and for the disposal of the contaminated absorbent.
  • the size of the portion of the absorbent passed through a solid bed containing an adsorbent is adjusted to keep the level of undesirable components low enough to avoid accumulation of the undesirable sulfur components and to allow the absorbent to perform its wash function.
  • the process and a plant operating there after are particularly suitable for use in the scrubbing of raw synthesis gas produced by gasification of coal or petroleum and as associated gases H 2 S, COS, HCN, NH 3 and thiols such as mercaptans, thioethers and / or thiophenes includes.
  • H 2 S, COS, HCN, NH 3 and thiols such as mercaptans, thioethers and / or thiophenes includes.
  • the washing of synthesis gas with highly volatile associated gases with a liquid, physically acting absorbent has long been proven, since the absorbent is easily regenerated by pressure reduction, flashing and / or heating.
  • the inventive, additional treatment of the absorbent with a solid adsorbent the applicability of the method is also extended to synthesis gas, which have larger amounts of heavy volatiles sulfur-containing associated gases.
  • the loaded bed When the adsorption capacity of the activated carbon bed is exhausted, the loaded bed is taken out of service and the loaded activated carbon is replaced by fresh coal.
  • the loaded bed can be regenerated with methanol vapor generated upon heating of the methanol.
  • the contaminated methanol vapor can be added to the gas stream expelled from the methanol at a suitable point.
  • the desorbing is preferably carried out by heating in a specially designed column, a so-called hot regenerator, and the solids bed containing the adsorbent is arranged downstream of the hot regenerator and is in fluid communication therewith.
  • the absorbent discharged from the hot regenerator is supplied to the solid-state bed containing the adsorbent in indirect heat exchange with the loaded absorbent supplied to the hot regenerator cooled.
  • the absorbent discharged from the hot regenerator is supplied to the solid-state bed containing the adsorbent in indirect heat exchange with the loaded absorbent supplied to the hot regenerator cooled.
  • a preferred embodiment of the invention is characterized in that deep-cooled methanol is used as absorption medium. This procedure is known and proven as Rectisol method. The high absorption capacity of the methanol at low temperatures is exploited. Therefore, the system must be equipped with a device for cooling the methanol and with appropriate insulation.
  • adsorbent activated carbon or a molecular sieve i. a granulate of artificially produced zeolites. Which adsorbent is used depends on the local availability and market prices and on the suitability for the particular synthesis gas and its associated gases.
  • a further preferred embodiment of the invention is that the system comprises a heat exchanger which is in fluid communication with the hot regenerator and the adsorption.
  • a heat exchange between the transferred from the flash tank in the hot generator and the transferred from the hot generator into the wash column absorbent is performed.
  • a further preferred embodiment of the invention is that it is the absorption medium is deeply cooled methanol and the system is equipped with a cooling unit for cooling the methanol and the deep-cooled Methanot-containing apparatuses are protected with insulating material to reduce cold losses.
  • the solid adsorbent is activated carbon or a molecular sieve.
  • Adsorbent depends on the local availability and market prices and on the suitability for the particular synthesis gas to be purified and its associated gases.
  • Raw synthesis gas 1 is cooled in heat exchanger 2 against the treated synthesis gas 3.
  • condensate 4 the resulting condensate 5 is deposited.
  • the crude synthesis gas is introduced into the scrubbing column 7.
  • the column is divided into three, one, trickle-containing washing stages. In the first stage 7a prewashing takes place, in the second 7b mainly H2S and in the third stage 7c mainly CO 2 is washed out.
  • the thus treated synthesis gas 3 then leaves the scrubbing column 7, is used in the heat exchangers 2 and 6 for cooling the crude synthesis gas 1 and then discharged from further treatment of the plant.
  • the only slightly loaded methanol 8, 9 is placed in the flash tank 10.
  • the carbon dioxide 12 is driven out of the methanol by pressure reduction and by flushing with nitrogen 11 and discharged for further treatment of the plant.
  • the thus pre-purified methanol 13 is then passed into the column 14, in which, by heating the methanol, mainly sulfur-containing associated gases 14 are expelled.
  • the expelled from the methanol, sulfur-containing associated gases 16 are from the plant for further treatment, eg. B. discharged in a Claus plant.
  • the methanol 17 desorbed in column 14 is returned to the wash column 7 for reuse via heat exchanger 18.
  • the streams 19 and 20 represent the top-down through the washing stages running methanol.
  • heat exchanger 18 a heat exchange between the pre-treated in the flash tank 10 methanol 13 and the further regenerated methanol 17 is performed.
  • a partial stream 21 is removed from the methanol 17 and treated in the adsorption plant 22 by passing the methanol through an activated carbon bed.
  • the adsorption plant 22 consists in this example of two parallel strands, so that, even when replacing or regenerating the activated carbon in one of the strands, the operation of the adsorption plant 22 can continue to run.
  • the partial stream 21 is then fed back into the methanol stream 17.
  • the invention provides an advantageous method which increases the service life of the absorbent and thus the economy of the absorption process.
  • the invention is therefore advantageously industrially applicable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Gas Separation By Absorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP17400026.5A 2017-05-12 2017-05-12 Procédé et installation destinés à séparer des gaz associés à partir de gaz brut de synthèse Withdrawn EP3401001A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP17400026.5A EP3401001A1 (fr) 2017-05-12 2017-05-12 Procédé et installation destinés à séparer des gaz associés à partir de gaz brut de synthèse
DE202017107744.6U DE202017107744U1 (de) 2017-05-12 2017-12-19 Anlage zur Abtrennung von Begleitgasen aus einem Rohsynthesegas
PCT/EP2018/025130 WO2018206154A1 (fr) 2017-05-12 2018-04-26 Processus et appareil destinés à séparer des gaz d'accompagnement d'un gaz de synthèse brut
CN201820691524.3U CN209242962U (zh) 2017-05-12 2018-05-10 用于从粗合成气流分离伴生气体的设备
CN201810441588.2A CN108863720A (zh) 2017-05-12 2018-05-10 从粗合成气分离伴生气体的方法和设备

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17400026.5A EP3401001A1 (fr) 2017-05-12 2017-05-12 Procédé et installation destinés à séparer des gaz associés à partir de gaz brut de synthèse

Publications (1)

Publication Number Publication Date
EP3401001A1 true EP3401001A1 (fr) 2018-11-14

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EP17400026.5A Withdrawn EP3401001A1 (fr) 2017-05-12 2017-05-12 Procédé et installation destinés à séparer des gaz associés à partir de gaz brut de synthèse

Country Status (4)

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EP (1) EP3401001A1 (fr)
CN (2) CN209242962U (fr)
DE (1) DE202017107744U1 (fr)
WO (1) WO2018206154A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112023646A (zh) * 2020-09-23 2020-12-04 南京九胜揽天科技有限公司 一种voc有机废气深度处理系统及工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114053824B (zh) * 2022-01-14 2022-05-24 德仕能源科技集团股份有限公司 一种从石油伴生气中回收二氧化碳的方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53149171A (en) * 1977-06-02 1978-12-26 Chiyoda Chem Eng & Constr Co Ltd Refining method for aqueous amine solution
EP0954369A1 (fr) * 1997-01-24 1999-11-10 MPR Services, Inc. Procede de traitement de gaz a l'aide d'amine ultra-appauvrie
US6334886B1 (en) * 2000-05-12 2002-01-01 Air Products And Chemicals, Inc. Removal of corrosive contaminants from alkanolamine absorbent process
DE60016899T2 (de) * 1999-03-12 2005-12-01 MPR Services, Inc., Dickinson Verfahren zum entfernen von kohlenwasserstoffen aus einem flüssigkeitsgemisch mit einem regenerierbaren filter
DE102006056117A1 (de) 2006-11-28 2008-05-29 Linde Ag Verfahren und Vorrichtung zur Abtrennung von Metallcarbonylen aus Synthesegas
US20100319254A1 (en) * 2009-06-17 2010-12-23 Thacker Pradeep S Methods and system for separating carbon dioxide from syngas
US20110081287A1 (en) * 2009-03-10 2011-04-07 Ifp Gas deacidizing method using an absorbent solution with vaporization and/or purification of a fraction of the regenerated absorbent solution
US20140252700A1 (en) * 2011-11-17 2014-09-11 Mitsubishi Heavy Industries, Ltd. Direct reduced iron manufacturing system

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6315398B1 (en) * 1992-10-21 2001-11-13 Xerox Corporation Thermal ink jet heater design

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53149171A (en) * 1977-06-02 1978-12-26 Chiyoda Chem Eng & Constr Co Ltd Refining method for aqueous amine solution
EP0954369A1 (fr) * 1997-01-24 1999-11-10 MPR Services, Inc. Procede de traitement de gaz a l'aide d'amine ultra-appauvrie
DE60016899T2 (de) * 1999-03-12 2005-12-01 MPR Services, Inc., Dickinson Verfahren zum entfernen von kohlenwasserstoffen aus einem flüssigkeitsgemisch mit einem regenerierbaren filter
US6334886B1 (en) * 2000-05-12 2002-01-01 Air Products And Chemicals, Inc. Removal of corrosive contaminants from alkanolamine absorbent process
DE102006056117A1 (de) 2006-11-28 2008-05-29 Linde Ag Verfahren und Vorrichtung zur Abtrennung von Metallcarbonylen aus Synthesegas
US20110081287A1 (en) * 2009-03-10 2011-04-07 Ifp Gas deacidizing method using an absorbent solution with vaporization and/or purification of a fraction of the regenerated absorbent solution
US20100319254A1 (en) * 2009-06-17 2010-12-23 Thacker Pradeep S Methods and system for separating carbon dioxide from syngas
US20140252700A1 (en) * 2011-11-17 2014-09-11 Mitsubishi Heavy Industries, Ltd. Direct reduced iron manufacturing system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Ullmann's Encyclopedia of Industrial Chemistry", vol. 15, pages: 367ff
"Ullmann's Encyclopedia of Industrial Chemistry", vol. 15, pages: 399 ff

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112023646A (zh) * 2020-09-23 2020-12-04 南京九胜揽天科技有限公司 一种voc有机废气深度处理系统及工艺

Also Published As

Publication number Publication date
WO2018206154A1 (fr) 2018-11-15
CN209242962U (zh) 2019-08-13
CN108863720A (zh) 2018-11-23
DE202017107744U1 (de) 2018-01-15

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